九、發明說明： 【發明所屬之技術領域】 本發明係涉及一種奈米碳管的生長方法，尤其涉及一 種低溫生長單壁奈米碳管的方法。 【先前技術】 單壁奈米石反管係廣泛應用於微電子、奈米器件、材料 合成、儲氫等許多領域。另，因單壁奈米碳管的埸發射域 值電壓大大低於多壁奈米碳管的埸發射域值電壓，故而採 用單壁奈米碳管作爲埸發射陰極的埸發射器件，可於較低 的電壓下工作’其功耗大大低於採用多壁奈米碳管作爲場 發射陰極的埸發射器件。 、按，先前技術中生長單壁奈米碳管的方法主要有電弧 法、鐳射蒸發法、太陽能法以及催化熱解法等。其中，較 為適合大規模生長奈米碳管的方法係催化熱解法，惟，該 類催化熱解法的反應溫度普遍較高。IX. Description of the Invention: [Technical Field] The present invention relates to a method for growing a carbon nanotube, and more particularly to a method for growing a single-walled carbon nanotube at a low temperature. [Prior Art] Single-walled nano-soil back pipe systems are widely used in many fields such as microelectronics, nanodevices, material synthesis, and hydrogen storage. In addition, since the 埸 emission domain voltage of a single-walled carbon nanotube is much lower than the 埸 emission domain voltage of a multi-walled carbon nanotube, a single-walled carbon nanotube is used as a ruthenium emission device of a ruthenium emission cathode. Operating at lower voltages, its power consumption is much lower than that of a multi-walled carbon nanotube used as a field emission cathode. According to the prior art, the method for growing single-walled carbon nanotubes mainly includes an arc method, a laser evaporation method, a solar energy method, and a catalytic pyrolysis method. Among them, the method suitable for large-scale growth of carbon nanotubes is catalytic pyrolysis, but the reaction temperature of such catalytic pyrolysis is generally high.
有鑒於此，確有必要提供一種低溫生長單壁奈米碳管 的方法。 U 【發明内容】 下面將藉由實施例進一步詳細說明一種單壁奈米碳管 的生長方法，該生長方法可於較低溫度下進行。 * -種單絲米碳管的“方法，該生長方法係包 下步騾： 提供一基底； 於基底上形成-氧化銅錫電極，該氧化銦锡電極的厚 1325018 - 度爲5奈米〜100奈米； 於氧化銦錫電極上沈積一鋁過渡層，該鋁過渡層的厚 • 度爲5奈米〜40奈米； 於叙過渡層上沈積一催化劑層，該催化劑層的厚度爲 3奈米〜1〇奈米； 將沈積有催化劑層、鋁過渡層及氧化銦錫電極的基底 放置於空氣中’於3G(TC〜50(TC下熱處理1()分鐘〜12小時， ^ 該催化劑層經退火後形成氧化顆粒； 將基底放置於反應裝置中，向反應裝置内通入保護氣 體，於保護氣體的保護下加熱至64(rc ~9〇(rc ;以及 通入碳源氣與保護氣體的混合氣體，加熱至 _ O’C反應3G分鐘〜6G分鐘生長出單壁奈米碳管。 與先前技術相較，本發明的單壁奈米碳管的生長方法 係於氧化銦錫電極及鋁過渡層上直接生長，且生長溫度較 低。 φ 【實施方式】 下面將結合附圖對本發明單壁奈米碳管的生長方法作 進一步的詳細說明。 本發明單壁奈米碳管的生長方法主要包括以下步驟： (一） 提供一矽或二氧化矽材料的基底1〇，如矽基底、 石英基底或者玻璃基底； (二） 於基底1〇上形成氧化銦錫電極2〇，該氧化銦 錫電極20的厚度爲5奈米〜1〇〇奈米； 氧化銦錫電極20可藉由光刻技術、電子束光刻技術結 8 1325018 . *反絲子雜技術、躲韻技錢者驗職技術於 . 基底10上形成，但不以此爲限。 藉由光刻技術形成氧化銦錫電極20的方法包括以下 步驟： 首先將基底10置於真空腔内，以氧化辞（Ζη〇χ)、鈮 酸鋰（UNbOx)、鈦酸鋰（LiTiOx)或者鈕酸鋰（LiTa〇x) 爲濺鍍靶材，以氬氣（Ar)與氧氣爲濺鍍氣體，於該基底 _ 1G的表㈣鍍—壓電_層，濺㈣方法可爲反應性直流 麟（Ddetive Sputtering)献紐射親鑛（RF Reactive Sputtering)，控制反應參數使得壓電薄膜層的 厚度約爲0· 02〜5微米；於壓電薄膜層表面塗覆一光阻層； 然後將-光罩罩於S阻層表面，該光罩的圖案與所需金屬 電極相對應；用雷射光或紫外光照射該光罩，於光阻表面 形成-曝光區；取下光罩後’將曝光的光阻層置於顯影液 内，去除曝光區的曝光光阻，露出部分壓電薄膜層；藉由 • 濺鍍法於剩餘光阻及露出的部分壓電薄膜層表面^一^化 銦錫層，該氧化銦錫層的厚度約爲5奈米〜1〇〇奈米；洗去 剩餘光阻及附著於光阻上的金屬膜層，剩餘的氧化鋼锡層 即形成所需的氧化銦錫電極2〇。 藉由濕法刻蝕技術形成氧化銦錫電極2〇的方法包括 以下步驟： 首先於基底10上藉由蒸鍍或濺射的方法形成—氧化 銦錫層，該氧化銦錫層的厚度約爲5奈米〜1〇〇奈米；將如 光致抗触劑的刻姓保護材料塗覆到氧化銦錫層的表面形成 9 1325018 相保稍，曝光或顯影去除賴保護層巾選定的部分， 二::擇的露出氧化銦錫層；將露出的氧化銦錫層與刻 =劑反應以便將其去除，其中，_劑以電解液的形式施 ^化予或化學地酿露Α的氧化銦錫層，電解液中包 '不：b X聰的方式與氧化銦錫層反應的中性鹽、酸或域 以刻財式與露出的氧化銦錫層反應的化學氧化 成刀藉由有機物⑸劑如純丙财機物賴去除剩餘的刻 • 悔護材料’刻钱保護材料下覆蓋的剩餘氧化銦錫層即形 成所需的氧化銦錫電極2〇。 (三） 於氧化銦錫電極20上藉由蒸鐘或者藏射的方法 形成-Μ 30作爲過渡層，該㈣渡層％的厚度爲 米〜40奈米，最優地，該㈣渡層3〇的厚度爲4〇奈米； (四） 於銘過渡層30上形成催化劑層4〇，催化劑可 選用鐵（Fe)、# (Co)、鎳（Ni)或者其任意組合的合金 之’該催化劑層40的厚度與選擇的催化劑麵相對應， 鲁 f選用鐵作爲催化劑時，鐵催化劑層的厚度爲3奈米〜1〇 奈米，優選地，鐵催化劑層的厚度爲5奈米； (五） 將沈積有催化劑層4〇、鋁過渡層3〇及金屬電 極20的基底1〇放置於空氣中，於3〇〇。心5〇〇。[下熱處理 10分鐘〜12小時，催化劑層4〇經退火後形成氧化顆粒； (六） 將基底ίο放置於適於化學氣相沈積（Chemical Vapor D印osition，CVD)反應的反應裝置（圖中未顯示） 中，向反應裝置内通入保護氣體，於保護氣體的保護下加 熱到一預定溫度，通入碳源氣與保護氣體的混合氣體，加 10 - ，至_1_。0反應3Q分鐘，分鐘從而生長出奈米碳 管50。 其中，預先通入保護氣體加熱到一預定溫度的作用係 防止催化劑層形成的氧化顆粒於奈来碳管5〇的生長過程 I進-步被氧化從而影響奈米碳管5〇的生長條件，該預定 ’皿度因使㈣催化劑種類的不同而不同，—般爲棚。c 750 C，當選麟作爲催化劑時，預定溫度優選爲65〇<>c， • 另，預先加熱時使用的保護氣體爲惰性氣體或氮氣 ，優選 地:保護氣體爲氬氣。於預先加熱過程後，可通入氫氣或 者氨氣還原催化劑層形成的氧化顆粒從而得到奈米級的催 化麵粒410，惟’於通入碳源氣加熱時，碳源氣分解亦 彳將氧化顆粒還原形成奈米級的催化劑顆粒彻，故而， 私氫氣或者氨氣還原的過程不是必須，可根據實際情況 選擇。碳源氣與保護氣體的混合氣體中的碳源氣爲碳氮化 ^物’可爲乙块、乙稀等，優選地，碳源氣爲乙块；保護 • 氣體=惰性氣體或者氮氣，優選地，保護氣體爲氬氣。 請參閱圖2 ’圖2係依據本發明單壁奈米碳管的生長 方法所得到的單壁奈米碳管的拉曼散射譜，其中於175咖_, 與300cm—1之間的-系列波學是單縣米碳管的呼吸模特往 峰。本實施例獲得拉曼散射譜的單壁奈米碳管的具體生長 步驟大致上包括：提供一玻璃基底；於玻璃基底上形成氧 化麵錫層，然後採用濕法刻紐術形成所需的氧化姻錫電 極，於氧化轉電極上減射厚度約I 4〇奈米的銘過渡層； 於錢渡層上濺射厚度約爲5奈米的鐵層作爲催化劑層 11 將沈積有鐵催化劑層、氧化銦錫電極及鋁過渡層的基底放 置於空氣中，約3〇〇°c下熱處理約1〇分鐘，退火後鐵催化 劑層形成氧化鐵顆粒；將帶有氧化鐵顆粒的基底放置於石 英反應舟中，將反應舟裝入管狀石英爐中央的反應室内， 通入氬氣加熱至約64(TC;通入氫氣使氧化鐵顆粒還原形 成奈米級的鐵催化劑顆粒；通入乙炔及氬氣的混合氣體， 加熱至約64(TC，反應約40分鐘生長出單壁奈米碳管。 凊參閱圖3及圖4，圖3係依據本發明實施例單壁奈 米碳官的生長方法得到的單壁奈米碳管的掃描電子顯微鏡 (Scanning Electron Microscope，SEM)照片；圖 4 係圖 3中單壁奈米碳管的高解析度的透射電子顯微鏡 (Transmission Electron Microscope，TEM)照、片。本實 施例獲仔的SEM'TEM照片中生長單壁奈米碳管的具體步驟 大致上包括：提供—絲底；於絲底上蒸鍍厚度約爲剛 奈米的氧化轉層’錢藉自齡刻倾娜成所需的氧 化銦錫電極；於氧化銦錫電極上錢射厚度約爲仙奈求的紹 過渡層；於㈣渡層上_厚度約爲5奈米的鐵層作爲催 化劑層，將沈積有賴化騎、氧化銦錫電極及铭過渡層 的基底放置於空氣中，約3G(TC下熱處理約1Q分鐘，退火 後鐵催化劑層形成氧化鐵顆粒：將帶有氧化鐵顆粒的基底 放^於石狀縣巾，將反應紐人管狀^紐中央的反 應，内，通人氬氣加熱簡;通人氫氣使氧化鐵顆 粒，原形成奈米_鐵催化_粒；通人乙炔及氬氣的混 合氣體’加熱至約74〇。〇反應約4〇分鐘生長出奈求碳管。 1325018 於未採用氧化銦錫電極或者紹過渡層而其他生長條件 壁奈米碳管的生長方法中的生長條件相同的先 則奈米Μ的生長方法中，僅發現多壁奈 現單壁奈米碳管。 、..不上所述’本發明確已符合發明專利之要件，遂依法 提出專利申請。惟，以上所述者僅為本發明之較佳實施例， 自不月b以此聞本案之中請專纖圍。舉凡熟悉本案技藝In view of this, it is indeed necessary to provide a method for growing a single-walled carbon nanotube at a low temperature. U [Summary of the Invention] A method of growing a single-walled carbon nanotube by a method which can be carried out at a lower temperature will be described in further detail by way of examples. * - "Method for monofilament carbon tube", the growth method is to pack a step: provide a substrate; form a copper oxide tin electrode on the substrate, the thickness of the indium tin oxide electrode is 1325018 - 5 nanometers ~ 100 nm; depositing an aluminum transition layer on the indium tin oxide electrode, the thickness of the aluminum transition layer is 5 nm to 40 nm; depositing a catalyst layer on the transition layer of the Syrian layer, the thickness of the catalyst layer is 3 Nano ~ 1 〇 nano; Place the substrate with the catalyst layer, aluminum transition layer and indium tin oxide electrode in the air '3G (TC~50 (TC heat treatment 1 () minutes ~ 12 hours, ^ the catalyst The layer is annealed to form oxidized particles; the substrate is placed in the reaction device, a protective gas is introduced into the reaction device, and heated to 64 (rc ~ 9 〇 (rc; and carbon source gas and protection) under the protection of the protective gas The mixed gas of the gas is heated to _O'C reaction for 3G minutes to 6G minutes to grow a single-walled carbon nanotube. Compared with the prior art, the growth method of the single-walled carbon nanotube of the present invention is based on an indium tin oxide electrode. Direct growth on the aluminum transition layer, and the growth temperature is lower. BEST MODE FOR CARRYING OUT THE INVENTION The method for growing a single-walled carbon nanotube of the present invention will be further described in detail below with reference to the accompanying drawings. The method for growing a single-walled carbon nanotube of the present invention mainly comprises the following steps: (1) providing a hydrazine or a dioxide a substrate of the germanium material, such as a germanium substrate, a quartz substrate or a glass substrate; (2) forming an indium tin oxide electrode 2 on the substrate 1 , the indium tin oxide electrode 20 having a thickness of 5 nm to 1 〇〇 The indium tin oxide electrode 20 can be formed by photolithography, electron beam lithography, 8 1325018 . * anti-filament hybrid technology, hiding rhyme technicians on the substrate 10, but not as The method for forming the indium tin oxide electrode 20 by photolithography includes the following steps: First, the substrate 10 is placed in a vacuum chamber to oxidize (Ζη〇χ), lithium niobate (UNbOx), lithium titanate (LiTiOx) Or Lithium Niobate (LiTa〇x) is a sputtering target, with argon (Ar) and oxygen as the sputtering gas, on the surface of the substrate _ 1G (four) plating - piezoelectric layer, splash (four) method can be the reaction Ddetive Sputtering offers RF Reactive Sputte Ring), controlling the reaction parameter such that the thickness of the piezoelectric film layer is about 0. 02~5 micrometers; coating a photoresist layer on the surface of the piezoelectric film layer; then covering the surface of the S resist layer with a mask, the mask The pattern corresponds to the desired metal electrode; the reticle is irradiated with laser light or ultraviolet light to form an exposure region on the surface of the photoresist; after the reticle is removed, the exposed photoresist layer is placed in the developer to remove the exposure. The exposure photoresist of the region exposes a portion of the piezoelectric film layer; the thickness of the indium tin oxide layer is about 5 by the sputtering method on the residual photoresist and the exposed portion of the piezoelectric film layer. Nano ~ 1 〇〇 nano; wash away the residual photoresist and the metal film layer attached to the photoresist, the remaining oxidized steel tin layer forms the desired indium tin oxide electrode 2 〇. The method for forming an indium tin oxide electrode by wet etching includes the following steps: First, an indium tin oxide layer is formed on the substrate 10 by evaporation or sputtering, and the thickness of the indium tin oxide layer is about 5 nm ~ 1 〇〇 nano; applying a protective material such as a photo-anti-contact agent to the surface of the indium tin oxide layer to form a 9 1325018 phase-preserving, exposure or development to remove the selected portion of the protective coating Second:: exposing the indium tin oxide layer; reacting the exposed indium tin oxide layer with the engraving agent to remove it, wherein the agent is applied in the form of an electrolyte or chemically deuterated indium oxide The tin layer, the electrolyte in the package 'no: b X Cong's way of reacting with the indium tin oxide layer of the neutral salt, acid or domain chemically oxidized by the chemical reaction with the exposed indium tin oxide layer by the organic matter (5) The agent, such as pure propylene, removes the remaining engraving material. The remaining indium tin oxide layer covered by the engraving material forms the desired indium tin oxide electrode. (3) Forming - Μ 30 as a transition layer on the indium tin oxide electrode 20 by means of a steaming clock or a trapping method, the thickness of the (four) crossing layer is m to 40 nm, and optimally, the (four) crossing layer 3 The thickness of the crucible is 4 nanometers; (4) the catalyst layer 4 is formed on the transition layer 30 of the Ming, and the catalyst may be selected from the alloys of iron (Fe), # (Co), nickel (Ni) or any combination thereof. The thickness of the catalyst layer 40 corresponds to the selected catalyst surface. When iron is used as the catalyst, the thickness of the iron catalyst layer is 3 nm to 1 nm, and preferably, the thickness of the iron catalyst layer is 5 nm; v) The substrate 1〇 on which the catalyst layer 4〇, the aluminum transition layer 3〇, and the metal electrode 20 are deposited is placed in the air at 3 Torr. Heart 5〇〇. [Unheating for 10 minutes to 12 hours, the catalyst layer 4 is annealed to form oxidized particles; (6) placing the substrate ίο in a reaction device suitable for chemical vapor deposition (CVD) reaction (in the figure) In the case where it is not shown, a protective gas is introduced into the reaction device, heated to a predetermined temperature under the protection of the shielding gas, and a mixed gas of the carbon source gas and the shielding gas is introduced, and 10 - to -_1_ is added. The reaction was carried out for 3 minutes, and then the carbon nanotubes 50 were grown. Wherein, the action of preheating the protective gas to a predetermined temperature prevents the oxidation particles formed by the catalyst layer from being oxidized in the growth process of the carbon nanotubes 5 to affect the growth conditions of the carbon nanotubes 5,, The predetermined 'span' varies depending on the type of catalyst (4), and is generally shed. c 750 C, when the lining is used as the catalyst, the predetermined temperature is preferably 65 〇 <> c, • Further, the shielding gas used in the preheating is an inert gas or nitrogen gas, preferably: the shielding gas is argon gas. After the pre-heating process, the oxidized particles formed by the reduction of the catalyst layer may be passed through hydrogen or ammonia gas to obtain a nano-sized catalytic surface 410, but the carbon source gas is decomposed and oxidized when heated by the carbon source gas. The reduction of the particles forms nanometer-sized catalyst particles. Therefore, the process of reducing hydrogen or ammonia gas is not necessary and can be selected according to actual conditions. The carbon source gas in the mixed gas of the carbon source gas and the shielding gas is a carbonitride material, which may be a block, an ethylene, etc., preferably, the carbon source gas is a block; protection • gas = inert gas or nitrogen, preferably Ground, the shielding gas is argon. Please refer to FIG. 2'. FIG. 2 is a Raman scattering spectrum of a single-walled carbon nanotube obtained by the growth method of the single-walled carbon nanotube according to the present invention, wherein the series is between 175 coffee and 300 cm-1. Waveology is the breathing model of a single county carbon tube. The specific growth step of the single-walled carbon nanotube obtained by the Raman scattering spectrum in this embodiment generally comprises: providing a glass substrate; forming an oxidized tin-plated layer on the glass substrate, and then forming the desired oxidation by wet engraving The tin electrode is used to reduce the thickness of the transition layer of about 4 μm on the oxidized electrode; the iron layer having a thickness of about 5 nm is sprayed on the Qiandu layer as the catalyst layer 11 and an iron catalyst layer is deposited thereon. The indium tin oxide electrode and the aluminum transition layer are placed in air, heat treated at about 3 ° C for about 1 minute, and the iron catalyst layer forms iron oxide particles after annealing; the substrate with iron oxide particles is placed in the quartz reaction. In the boat, the reaction boat is loaded into the reaction chamber in the center of the tubular quartz furnace, and heated to about 64 (TC; THF; hydrogen is passed to reduce the iron oxide particles to form nano-sized iron catalyst particles; acetylene and argon are introduced. The mixed gas is heated to about 64 (TC, and the reaction grows for about 40 minutes to grow a single-walled carbon nanotube. 凊 See FIG. 3 and FIG. 4, FIG. 3 is a method for growing a single-walled nanocarbon according to an embodiment of the present invention. Single-walled carbon nanotube Scanning Electron Microscope (SEM) photograph; Fig. 4 is a high-resolution transmission electron microscope (TEM) photograph and sheet of a single-walled carbon nanotube in Fig. 3. The SEM of this example was obtained. The specific steps for growing a single-walled carbon nanotube in a TEM photograph generally include: providing a silk bottom; evaporating an oxidized transfer layer having a thickness of about nanometer on the silk bottom. Indium tin oxide electrode; the thickness of the injecting tin oxide on the indium tin oxide electrode is about the transition layer of Sennai; on the (four) crossing layer, the iron layer with a thickness of about 5 nm is used as the catalyst layer, and the Laihua rider will be deposited. The indium tin oxide electrode and the substrate of the transition layer are placed in air at about 3G (heat treatment at TC for about 1Q minutes, and the iron catalyst layer forms iron oxide particles after annealing: the substrate with iron oxide particles is placed on the stone-like county towel It will react with the reaction of the central tube of the New Zealand tube, and it will be heated by the argon gas; the hydrogen can be used to make the iron oxide particles, which form the nano-iron catalyst_particle; the mixture of acetylene and argon is heated. To about 74 〇. 〇 reaction about 4 〇 The bell grows out of the carbon tube. 1325018 In the growth method of the first nematox which has the same growth conditions in the growth method of the indium tin oxide electrode or the transition layer and other growth conditions, the carbon nanotubes are only found in the growth method. Multi-walled N-phase single-walled carbon nanotubes.., not the above description. The present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention. Since the month of the b, please listen to the case in this case, please specialize in the case.
=人士援依本發明之精神所作之等效修贼變化，皆應涵 蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1係本發明單壁奈米碳管的生長方法的流程示 意圖。 圖2係依據本發明單壁奈米碳管的生長方法所得 到的單壁奈米碳管的拉曼散射譜。= The equivalent of the thief change made by the person in accordance with the spirit of the present invention shall be within the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart showing a method of growing a single-walled carbon nanotube of the present invention. Fig. 2 is a Raman scattering spectrum of a single-walled carbon nanotube obtained by a method for growing a single-walled carbon nanotube according to the present invention.
圖3係依據本發明單壁奈米碳管的生長方法得到 的單壁奈米碳管的掃描電子顯微鏡（ScanningFigure 3 is a scanning electron microscope (Scanning) of a single-walled carbon nanotube obtained by the growth method of a single-walled carbon nanotube according to the present invention.
Electron Microscope，SEM)照片。 圖4係圖3中單壁奈米碳管的高解析度的透射電 子顯微鏡（Transmission Electron Microscope，TEM) 照片。 【主要元件符號說明】 場發射陰極 1〇〇 基底 10 氧化銦錫電極 20 13 1325018 鋁過渡層 30 催化劑層 40 催化劑顆粒 410 單壁奈米碳管 50Electron Microscope, SEM) photo. Fig. 4 is a high-resolution transmission electron microscope (TEM) photograph of the single-walled carbon nanotube of Fig. 3. [Main component symbol description] Field emission cathode 1〇〇 Substrate 10 Indium tin oxide electrode 20 13 1325018 Aluminum transition layer 30 Catalyst layer 40 Catalyst particles 410 Single-walled carbon nanotubes 50